JP6276958B2 - Composite polyester composition and lubricant - Google Patents

Description

  The present invention relates to a composite polyester composition and a lubricant. Specifically, the present invention provides a composite polyester composition containing a polyester obtained by condensing two or more polyhydric alcohols, a polyvalent carboxylic acid, and a monohydric alcohol, and the composite polyester composition. Containing lubricant.

  Lubricants generally include base oils and various additives. Base oils include mineral oils obtained from crude oils, chemically synthesized ester oils, fluorine oils, polyalphaolefin oils, and the like. Among these, ester oils are suitably used for jet aircraft, automobile engine oils, greases and the like because of their low pour point, high viscosity index, high flash point, good lubricating performance, biodegradability, and the like.

  As ester oil, monoester obtained from reaction of aliphatic monocarboxylic acid and monohydric alcohol; diester obtained from reaction of aliphatic dibasic acid and monohydric alcohol; polyhydric alcohol and aliphatic carboxylic acid; Various esters are disclosed (Patent Documents 1 to 5), such as esters obtained from the above reaction; and complex esters obtained from reaction with polyols, polybasic acids, and aliphatic monocarboxylic acids.

  Patent Documents 6 and 7 disclose polyester compositions obtained from the reaction of polyhydric alcohols, polycarboxylic acids, and monohydric alcohols. In Patent Document 6, dimer acid or trimer acid is used as the polyvalent carboxylic acid, and divalent alcohol is mainly used as the polyhydric alcohol. In Patent Document 7, trihydric or higher alcohols are mainly used as polyhydric alcohols. In these documents, it is proposed to improve the lubricating performance by using the above polyester composition as a lubricant.

JP 2002-097482 A JP 2005-154726 A JP 2005-232434 A JP 2005-213377 A JP 2005-232470 A JP-A-61-213296 JP 2010-150495 A

  In recent years, with the diversification and sophistication of industrial fields, lubricants are required to have high lubrication performance. For this reason, development of a polyester composition having lower frictional properties and capable of exhibiting excellent lubrication performance is required, and by improving the polyester composition used for the lubricant, the lubrication performance can be improved. It is being considered.

  Moreover, the polyester composition obtained by the prior art may not have sufficient dispersibility in the base oil when used as a lubricant. That is, the conventional polyester composition has a problem that it is difficult to achieve both lubrication performance and dispersibility. For this reason, there has been a demand for a polyester composition that exhibits excellent lubricating performance and is excellent in dispersibility in base oil.

  Accordingly, the present inventors provide a polyester composition that is capable of exhibiting excellent lubrication performance and is excellent in dispersibility in a base oil in order to solve such problems of the prior art. We proceeded with a study for this purpose.

As a result of intensive studies to solve the above problems, the present inventors include a polyester obtained by condensing two or more polyhydric alcohols, polyhydric carboxylic acids, and monohydric alcohols. In the composite polyester composition, at least one of the two or more polyhydric alcohols is a polyhydric alcohol containing three or more hydroxyl groups, thereby improving the lubricating performance of the composite polyester composition and the dispersibility in the base oil. Found to get.
Specifically, the present invention has the following configuration.

[1] A polyester obtained by condensing two or more polyhydric alcohols, a polyvalent carboxylic acid, and a monohydric alcohol, and at least one of the two or more polyhydric alcohols is 3 A composite polyester composition, which is a polyhydric alcohol containing the above hydroxyl group.
[2] The composite polyester composition according to [1], wherein at least one of the two or more polyhydric alcohols is a saturated aliphatic alcohol.
[3] The composite polyester composition according to [1] or [2], wherein at least one of the two or more polyhydric alcohols is selected from pentaerythritol, trimethylolpropane, glycerin, or dipentaerythritol.
[4] The two or more kinds of polyhydric alcohols include a first polyhydric alcohol containing 3 to 6 hydroxyl groups and a second polyhydric alcohol containing 2 to 6 hydroxyl groups. [3] The composite polyester composition according to any one of [3].
[5] The first polyhydric alcohol is a polyhydric alcohol containing 3 or 4 hydroxyl groups, and the second polyhydric alcohol is a polyhydric alcohol containing 2 to 4 hydroxyl groups [4] ] The composite polyester composition as described in.
[6] The composite polyester composition according to any one of [1] to [5], wherein the polyvalent carboxylic acid has 10 or more carbon atoms.
[7] The composite polyester composition according to any one of [1] to [6], wherein the polyvalent carboxylic acid has 24 to 48 carbon atoms.
[8] The composite polyester composition according to any one of [1] to [7], wherein the polyvalent carboxylic acid is a dibasic acid or a tribasic acid of an unsaturated fatty acid.
[9] The composite polyester composition according to any one of [1] to [8], wherein the polyvalent carboxylic acid is dimer acid, trimer acid, or erucic acid dimer.
[10] The composite polyester composition according to any one of [1] to [9], wherein the monohydric alcohol has 6 or more carbon atoms.
[11] The composite polyester composition according to any one of [1] to [10], wherein the monohydric alcohol has at least one oxyalkylene group.
[12] The composite polyester composition according to any one of [1] to [11], wherein the monohydric alcohol is represented by the following general formula (1).
(In general formula (1), R ^a has an alkyl group which may have ^a substituent, ^a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An aryl group which may be substituted or a heteroaryl group which may have a substituent, wherein X ^a1 and X ^a2 each independently represents a hydrogen atom, a halogen atom or an alkyl group, and na 1 represents an integer of 1 to 4. Na2 represents an integer of 1 to 12. When na1 is 2 or more, the na1 X ^a1 may be the same or different, and the na1 X ^a2 may be the same or different. In addition, when na2 is 2 or more, na2 — (O (CX ^a1 X ^a2 ) _na1 — may be the same or different).
[13] The composite polyester composition according to any one of [1] to [12], further including at least one organometallic compound of an organomolybdenum compound and an organozinc compound.
[14] The organometallic compound includes sulfurized oxymolybdenum-N, N-di-octyldithiocarbamate, sulfurized oxymolybdenum-N, N-di-tridecyldithiocarbamate, zinc n-butyl-n-pentyldithiophosphate, di- The composite polyester composition according to [13], which is zinc 2-ethylhexyldithiophosphate or zinc isopropyl-1-ethylbutyldithiophosphate.
[15] The polyester is mixed and condensed so that the equivalent ratio of the polyhydric carboxylic acid is 1 to 4 and the equivalent ratio of the monohydric alcohol is 0.5 to 5 with respect to the polyhydric alcohol. The composite polyester composition according to any one of [1] to [14], which is obtained by the process.
[16] The polyester is mixed so that the equivalent ratio of the polyhydric carboxylic acid is 2.2 to 4 and the equivalent ratio of the monohydric alcohol is 2.5 to 5 with respect to the polyhydric alcohol. The composite polyester composition according to any one of [1] to [15], obtained by condensation.
[17] The composite polyester according to any one of [1] to [16], wherein the polyester includes a polyester represented by the following general formula (3) and a polyester represented by the following general formula (4). Composition.
(In general formula (3), R represents an n-valent atomic group, R ¹ represents a (m + 1) -valent chain-like or cyclic aliphatic linking group or aromatic linking group, and R ² has a substituent. An alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an alkenyl group that may have a substituent, an aryl group that may have a substituent, or a hetero that may have a substituent Represents an aryl group, m represents an integer of 1 to 3, and when m is 2 or more, m R ^{2 s} may be the same or different, and n represents an integer of 3 to 6 , N -OCOR ^1- (COOR ² ) _m may be the same or different.)
(In General Formula (4), R ′ represents an n-valent atomic group, R ³ represents an (m + 1) -valent chain-like or cyclic aliphatic linking group or aromatic linking group, and R ⁴ represents a substituent. It may have an alkyl group that may have, a cycloalkyl group that may have a substituent, an alkenyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. Represents a heteroaryl group, m represents an integer of 1 to 3, and when m is 2 or more, m R ^{4 s} may be the same or different, and n represents an integer of 2 to 6 N-OCOR ³ — (COOR ⁴ ) _m may be the same or different, and R in the general formula (3), R ′ in the general formula (4), and the general formula ( 3) R ¹ in general formula (4), R ³ in general formula (4), R ² in general formula (3) and R ⁴ in general formula (4) are different.
[18] In the general formulas (3) and (4), R and R ′ are each independently an atomic group composed of a saturated aliphatic hydrocarbon which may have a substituent. Polyester composition.
[19] In the above general formulas (3) and (4), R ¹ and R ³ are each independently a dimer acid residue, a trimer acid residue or an erucic acid dimer residue. The composite polyester composition described.
[20] The composite polyester according to any one of [17] to [19], wherein in the general formulas (3) and (4), R ² and R ⁴ are each independently a group having an oxyalkylene structure. Composition.
[21] The composite polyester composition according to any one of [1] to [20], wherein the viscosity at 40 ° C. is 50 to 1650 mPas.
[22] The composite polyester composition according to any one of [1] to [21], an antiwear agent, a viscosity index improver, an antioxidant, a detergent, a dispersant, a flow, a curing agent, and corrosion prevention. A composition containing one or more additives selected from an agent, a seal compatibility agent, an antifoaming agent, a rust inhibitor, a corrosion inhibitor, a friction modifier, and a thickener.
[23] The composite polyester composition according to any one of [1] to [21], or the composition according to [22], a mineral oil, a fat compound, a polyolefin oil, a silicone oil, and a perfluoropolyether. A composition comprising at least one or more media selected from oils, aromatic ester oils, and polyol ester lubricating oils.
[24] A lubricant comprising the composite polyester composition according to any one of [1] to [21], or the composition according to [22] or [23].
[25] Grease lubricating oil, mold release agent, engine oil for internal combustion engine, oil for metal processing (cutting), oil for bearing, fuel for combustion engine, vehicle engine oil, gear oil, hydraulic oil for automobile, Aircraft lubricant, machine oil, turbine oil, bearing oil, hydraulic fluid, compressor / vacuum pump oil, refrigeration oil, metalworking lubricant, magnetic recording medium lubricant, micromachine lubricant, artificial bone The lubricant according to [24], which is used as a lubricant, shock absorber oil or rolling oil.

  According to the present invention, a composite polyester composition capable of exhibiting excellent lubricating performance can be obtained. Furthermore, the composite polyester composition of the present invention can exhibit excellent dispersibility with respect to the base oil. Thus, the composite polyester composition of the present invention has high lubricating performance and dispersibility.

  Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

(Composite polyester composition)
The present invention relates to a composite polyester composition containing a polyester obtained by condensing two or more kinds of polyhydric alcohols, polyhydric carboxylic acids, and monohydric alcohols. Here, at least one of the two or more polyhydric alcohols is a polyhydric alcohol containing three or more hydroxyl groups. The polyhydric alcohol is an alcohol having at least two hydroxyl groups, and the polyhydric carboxylic acid is a carboxylic acid having at least two carboxyl groups. In the present invention, by synthesizing a polyester using such a specific polyhydric alcohol, it is possible to improve the dispersibility in a base oil and to obtain a composite polyester composition that exhibits high lubricating performance. .

<Polyhydric alcohol>
The polyhydric alcohol used for polyester condensation is a compound containing at least two hydroxyl groups. The polyhydric alcohol is represented by R (OH) _n . R is an n-valent aliphatic, alicyclic or aromatic ring group, and one or more carbon atoms not adjacent to each other in R may be substituted with an oxygen atom. Among these, R is preferably an aliphatic group.

R is preferably an n-valent aliphatic group containing 2 to 20, more preferably 2 to 15, still more preferably 2 to 10, still more preferably 2 to 7, particularly preferably 3 to 5 carbon atoms. . However, it is not limited to this range, and depending on the application, it may be preferable that the number of carbon atoms is rather large.
Preferred examples of R are satisfied _{C x H 2X + 2-n} (x is a number from 2 to 20) or _{C x H 2X + 2-n} O m (x 2 to 20 number, m is m <x More preferably a group represented by m ≦ x / 2.

  Two or more kinds of polyhydric alcohols are used for the condensation of the composite polyester composition of the present invention, and at least one of the two or more kinds of polyhydric alcohols contains three or more hydroxyl groups. In two or more types of polyhydric alcohols, the number of hydroxyl groups may be the same or different.

  Of the two or more polyhydric alcohols, at least one is preferably a saturated aliphatic alcohol. Further, the saturated aliphatic alcohol used in the present invention preferably has a branched structure. In addition, it is preferable that carbon number of saturated aliphatic alcohol is 3-20, and it is more preferable that it is 3-15.

  Examples of the polyhydric alcohol that can be used in the present invention include the following compounds. Diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 1,4-dimethylolcyclohexane, neopentyl glycol; trimethylolmethane, trimethylolethane , Triols such as trimethylolpropane, trimethylolbutane, glycerol; tetraols such as trimethylolpropane, multiols such as dipentaerythritol, tripentaerythritol; xylitol, sorbitol, mannitol, erythritol, maltitol, isomalt, Sugar alcohols such as albinitol, ribitol, iditol, boremitol, and periseitol; and sugars such as glucose; and the like. Among these, neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, glycerin, pentaerythritol, dipentaerythritol, and xylitol are preferable; trimethylol propane, trimethylol butane, glycerin, pentaerythritol, and dipentayl. Erythritol and the like are more preferable; trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol and the like are still more preferable; pentaerythritol and trimethylolpropane are particularly preferable. These do not need to be high-purity products, and are preferably used even in so-called industrial brands. For example, an industrial brand of pentaerythritol is said to consist of about 88% mono-, 10% di- and 1-2% tri-pentaerythritol. In the present invention, an industrial brand such as pentaerythritol is used in the present invention. It can be used as a polyhydric alcohol.

It is preferable that 2 or more types of polyhydric alcohol contains the 1st polyhydric alcohol containing 3-6 hydroxyl groups, and the 2nd polyhydric alcohol containing 2-6 hydroxyl groups. The first polyhydric alcohol more preferably contains 3 to 5 hydroxyl groups, and more preferably 3 or 4 hydroxyl groups. Further, the second polyhydric alcohol preferably contains 2 to 4 hydroxyl groups, and more preferably contains 3 or 4 hydroxyl groups. The number of hydroxyl groups contained in the first polyhydric alcohol and the second polyhydric alcohol may be the same or different from each other as long as the number is within the above range. .
In addition, when 2 or more types of polyhydric alcohol contains 3 or more types of polyhydric alcohol, in addition to 1st polyhydric alcohol and 2nd polyhydric alcohol, other polyhydric alcohol (3rd polyhydric alcohol) Alcohol).

  In this invention, as above-mentioned, the dispersibility to the base oil of a composite polyester composition can be improved by using multiple types of polyhydric alcohol. This is considered to be because the shape of the polyester obtained by condensation can be diversified by using multiple types of polyhydric alcohols used for polyester condensation. In the present invention, the polyhydric alcohol forms the core part (central atomic group) of the polyester, and the shape of the polyester can be more effectively diversified by diversifying the shape of the core part. It becomes. Thus, it is considered that by diversifying the shape of the polyester, the packing between the polyesters can be suppressed and the dispersibility with respect to the base oil can be enhanced.

  Specific examples of the polyhydric alcohol that can be used in the present invention are shown below, but the present invention is not limited thereto. In the present invention, it is preferable to select a plurality of types from the following specific examples and use them for condensation of polyester.

<Polyvalent carboxylic acid>
The polyvalent carboxylic acid used for the condensation of the polyester is a compound containing at least two carboxyl groups. It is preferable that 2-4 carboxyl groups are contained in one molecule, and it is more preferable that 2 or 3 carboxyl groups are contained in one molecule. As the polyvalent carboxylic acid used in the present invention, any one of divalent to tetravalent polyvalent carboxylic acids may be used, or a plurality of types may be used. For example, a mixture of a divalent carboxylic acid and a trivalent carboxylic acid may be used, or a mixture of a divalent carboxylic acid, a trivalent carboxylic acid, and a tetravalent carboxylic acid may be used, A mixture of a trivalent carboxylic acid and a tetravalent carboxylic acid may be used.

  The number of carbon atoms of the polyvalent carboxylic acid is preferably 7 or more, more preferably 10 or more, preferably 12 or more, more preferably 18 or more, and further preferably 24 or more. preferable. Further, the carbon number of the polyvalent carboxylic acid is preferably 66 or less, more preferably 60 or less, and further preferably 48 or less. Especially, it is especially preferable that carbon number of polyvalent carboxylic acid is 24-48. In the present invention, the carbon number of the polyvalent carboxylic acid represents the number of carbon atoms including the carbon atom constituting the carboxyl group. Thus, the lubricity performance of a composite polyester composition can be improved more by making carbon number of polyhydric carboxylic acid in the said range.

  The carboxyl groups in the molecule are linked by a chain or cyclic divalent or higher aliphatic hydrocarbon or aromatic hydrocarbon. One or more carbon atoms not adjacent to each other of the carbon atoms of the aliphatic hydrocarbon or aromatic hydrocarbon linking group may be substituted with oxygen atoms. Especially, in this invention, it is preferable that the group which connects the carboxyl group in a molecule | numerator is a C20-C46 aliphatic hydrocarbon.

  The aliphatic hydrocarbon that connects the carboxyl groups in the molecule of the polyvalent carboxylic acid preferably contains an unsaturated bond. That is, the polyvalent carboxylic acid is preferably an unsaturated fatty acid, more preferably a dibasic acid or a tribasic acid of an unsaturated fatty acid.

  Examples of the polyvalent carboxylic acid that can be used in the present invention include terephthalic acid, phthalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, and trimellitic acid. , Dimer acid, trimer acid, erucic acid dimer, and the like. Of these, dimer acid, trimer acid, and erucic acid dimer are preferably used. The dimer acid, trimer acid, and erucic acid dimer may be hydrogenated.

Here, the dimer acid is an aliphatic or alicyclic dicarboxylic acid produced by dimerization of an unsaturated fatty acid (usually 18 carbon atoms) by polymerization or Diels-Alder reaction (in addition to most dimers, Many of them contain trimers, monomers and the like of several mol%), and among them, those whose main components are trimers are defined as trimer acids.
As specific examples of dimer acid or trimer acid, Tsunodim (registered trademark) 205, 216, 228, and 395 manufactured by Tsukino Food Industry Co., Ltd. can be exemplified as dimer acid, and tunodim 345 and the like can be exemplified as trimer acid. Other products manufactured by Cognis and Unikema are also included.

  The erucic acid dimer is a dicarboxylic acid having 44 carbon atoms obtained by dimerizing an unsaturated fatty acid (erucic acid) having 22 carbon atoms. Examples of erucic acid preferably used for dimerization of erucic acid dimer include compounds such as CAS No. 112-86-7. Further, as a typical erucic acid dimer, there is a trade name Pripol 1004 (manufactured by Croda).

  In the present invention, polyhydric carboxylic acid anhydrides can be used in place of polycarboxylic acids. The polyhydric carboxylic acid anhydride is a product obtained by intramolecular or intermolecular dehydration condensation of two COOHs of the above polycarboxylic acid. The preferred form is the same as above. Examples of the anhydrides include succinic anhydride, glutaric anhydride, adipic anhydride, maleic anhydride, phthalic anhydride, nadoic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride and mixed polybasic anhydride Things are included.

  Specific examples of the polyvalent carboxylic acid that can be used in the present invention are shown below, but the present invention is not limited thereto.

<Monohydric alcohol>
The monohydric alcohol used for polyester condensation is a compound containing one hydroxyl group in one molecule. A monohydric alcohol is represented by R (OH). R is a monovalent aliphatic, alicyclic or aromatic ring group. R preferably has 3 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more. By setting the carbon number of the monohydric alcohol within the above range, the monohydric alcohol can be prevented from evaporating during the condensation reaction, and the polyester condensation reaction can be efficiently advanced.

  The monohydric alcohol preferably has at least one oxyalkylene group. An oxyalkylene group refers to a structure in which an oxygen atom is introduced into an alkylene chain. The alkylene chain may be linear, branched or cyclic. Moreover, 1-10 are preferable, as for carbon number of an alkylene chain, 2-8 are more preferable, and 2-4 are more preferable. Moreover, 1-10 are preferable, as for the oxygen number introduce | transduced, 1-6 are preferable, and 1-4 are more preferable.

  The monohydric alcohol used in the present invention is preferably one represented by the following general formula (1).

Here, in the general formula (1), Ra represents an alkyl group which may have ^a substituent, ^a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. An aryl group which may have or a heteroaryl group which may have a substituent, and X ^a1 and X ^a2 each independently represent a hydrogen atom, a halogen atom or an alkyl group; Na1 represents an integer of 1 to 4, and na2 represents an integer of 1 to 12. When na1 is 2 or more, na1 X ^a1 may be the same or different, and na1 X ^a2 may be the same or different. When na2 is 2 or more, na2-(O (CX ^a1 X ^a2 ) _na1 -may be the same or different.

That the number of carbon atoms of the alkyl moiety of the alkyl group which may have a substituent represented by R ^a is preferably 3 to 17, more preferably from 4 to 13, 5 to 9 Is more preferable. The alkyl group represented by R ^a may be linear or branched. R ^a may be a cycloalkyl group.

The number of carbon atoms of the alkenyl group moiety alkenyl group which may have a substituent represented by R ^a is preferably 3 to 17, more preferably from 4 to 13, 5 to 9 Is more preferable. The alkyl group represented by R ^a may be linear, branched or cyclic.

The number of carbon atoms of the aryl moiety of the aryl group or heteroaryl group which may have a substituent represented by R ^a is preferably 6 to 17, and more preferably 6-12. Examples of the aryl group represented by ^Ra include a phenyl group and a naphthyl group, and among them, a phenyl group is particularly preferable. Examples of the heteroaryl group represented by ^Ra include imidazolyl, pyridyl, quinolyl, furyl, thienyl, benzoxazolyl, indolyl, benzimidazolyl, benzthiazolyl, carbazolyl, azepinyl Can be illustrated. The hetero atom contained in the heteroaryl group is preferably an oxygen atom, a sulfur atom, or a nitrogen atom, and more preferably an oxygen atom.

Especially, in General formula (1), it is more preferable that ^Ra is an alkyl group which may have ^a substituent. Here, the alkyl group may be a branched alkyl group. More preferably, X ^a1 and X ^a2 are each independently a hydrogen atom or an alkyl group.

  In general (1), na1 is more preferably an integer of 1 to 3, and further preferably 1 or 2. Na2 is more preferably an integer of 1 to 8, more preferably an integer of 1 to 6, and particularly preferably an integer of 1 to 3.

  The number of carbon atoms of the monohydric alcohol represented by general formula (1) is preferably 3 or more, more preferably 6 or more, and still more preferably 8 or more. By using such a monohydric alcohol, volatilization of the monohydric alcohol during the condensation reaction can be suppressed, and the polyester condensation reaction can be efficiently advanced.

Examples of the substituent that R ^a may have include a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms (for example, methyl, ethyl, which are both linear or branched propyl, butyl, Pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, or tetracosyl); alkenyl having 2 to 35 carbon atoms Groups (eg, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl); cycloalkyl groups having 3 to 10 carbon atoms (eg, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl) Cycloheptyl); an aromatic ring group having 6 to 30 carbon atoms (for example, phenyl, naphthyl, biphenyl, phenanthryl, anthracenyl), a heterocyclic group (nitrogen atom, oxygen atom, and sulfur atom) Preferably a heterocyclic residue containing an atom, for example pyridyl, pyrimidyl, triazinyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, imidazolyl, oxazolyl, thiadialyl, oxadiazolyl, quinolyl, isoquinolyl); A group consisting of a combination thereof is represented. If possible, these substituents may further have one or more substituents. Examples of the substituents include alkoxy groups, alkoxycarbonyl groups, halogen atoms, ether groups, alkylcarbonyl groups, cyano groups. Group, thioether group, sulfoxide group, sulfonyl group, amide group and the like.

  Specific examples of the monohydric alcohol that can be used in the present invention are shown below, but the present invention is not limited thereto.

(Organic metal compound)
The composite polyester composition of the present invention may further contain at least one organometallic compound of an organomolybdenum compound and an organozinc compound in addition to the polyester obtained by reacting and condensing each compound described above.

  Examples of the organic molybdenum compound used in the present invention include sulfur-containing organic molybdenum compounds such as molybdenum dithiophosphate (sometimes referred to as MoDTP) and molybdenum dithiocarbamate (sometimes referred to as MoDTC); inorganic molybdenum compounds (for example, Molybdenum oxide such as molybdenum dioxide and molybdenum trioxide, orthomolybdic acid, paramolybdic acid, molybdic acid such as (poly) sulfurized molybdic acid, metal salts of these molybdic acids, molybdate such as ammonium salts, molybdenum disulfide, Molybdenum sulfide such as molybdenum trisulfide, molybdenum pentasulfide, and polysulfide molybdenum, molybdenum sulfides, metal salts of molybdenum sulfides or amine salts, molybdenum halides such as molybdenum chloride, and the like; sulfur-containing organic compounds (eg, alkyl (Thio) xanthate, thiadiazole, mercaptothiadiazole, thiocarbonate, tetrahydrocarbyl thiuram disulfide, bis (di (thio) hydrocarbyl dithiophosphonate) disulfide, organic (poly) sulfide, sulfide ester, etc.) or other organic compounds A complex with molybdenum, or a complex of a sulfur-containing molybdenum compound such as molybdenum sulfide or sulfurized molybdate with an alkenyl succinimide can be used.

  As the organic molybdenum compound, an organic molybdenum compound that does not contain sulfur as a constituent element can be used. Specific examples of organic molybdenum compounds that do not contain sulfur as a constituent element include molybdenum-amine complexes, molybdenum-succinimide complexes, molybdenum salts of organic acids, and molybdenum salts of alcohols. Complexes, molybdenum salts of organic acids and molybdenum salts of alcohols are preferred.

As a method for producing the MoDTP, for example, the methods described in JP-A Nos. 61-87690 and 61-106687 are preferably used. That is, it can be obtained by reacting molybdenum trioxide or molybdate with alkali sulfide or alkali hydrosulfide, and then adding P ₂ S ₅ and secondary alcohol and reacting them at an appropriate temperature. As a method for producing MoDTC, for example, the method described in Japanese Patent Publication No. 56-12638 is preferably used. That is, it can be obtained by reacting molybdenum trioxide or molybdate with alkali sulfide or alkali hydrosulfide, then adding carbon disulfide and secondary amine and reacting them at an appropriate temperature.

  Zinc dithiophosphate (ZDTP), which is an organozinc compound used in the present invention, is represented by the general formula (2).

In general formula (2), Q ¹ , Q ² , Q ³ , and Q ⁴ may be the same or different and are each independently isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, hexyl. An alkyl group having 4 to 20 carbon atoms such as a group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, mistyl group, palmityl group, stearyl group, etc. It is preferable to represent.

The organometallic compound may comprise a metal salt or a metal-ligand complex. Here, the metal is preferably molybdenum or zinc. Ligand includes alcohol, polyol, glycerol, partial ester glycerol, thiol, carboxylate, carbamate, thiocarbamate, dithiocarbamate, phosphate, thiophosphate, dithiophosphate, amide, imide, amine, thiazole, thiadiazole, dithiazole, diazole , Hydrocarbyl derivatives of triazole, and other polar molecular functional groups containing effective amounts of O, N, S or P individually or in combination. For example, sulfurized oxymolybdenum -N, N-di - octyl dithiocarbamate _{(C 8 -Mo (DTC))} , sulfurized oxymolybdenum -N, N-di - tridecyl dithiocarbamate _{(C 16 -Mo (DTC))} , n - butyl -n- pentyl zinc dithiophosphate _{(C 4 / C 5 ZnDTP)} , with di-2-ethylhexyl dithiophosphate, zinc (C ₈ ZnDTP) or isopropyl-1-ethyl butyl zinc dithiophosphate (C ₃ / C ₆ ZnDTP) Preferably there is. Other examples include Mo-containing compounds such as Mo-dithiophosphate [Mo (DTP)], Mo-amine [Mo (Am)], Mo-alcolate, and Mo-alcohol-amide.

  In the composite polyester composition of the present invention, when an organic molybdenum compound is used, the content is preferably 10 to 1000 ppm, more preferably 50 to 800 ppm, based on the total mass of the composition. Preferably, it is more preferably 100 to 600 ppm. Moreover, when using an organic zinc compound, it is preferable that the content is contained 0.01-5 mass% with respect to the composition total mass, and it is more contained 0.05-3 mass%. Preferably, 0.08 to 1% by mass is contained. By making content of an organometallic compound in the said range, stability of a composite polyester composition can be improved and it becomes possible to exhibit more superior lubricating performance.

(Other compounds)
In the present invention, in addition to the polyhydric alcohol, polyhydric carboxylic acid and monohydric alcohol, other components may be used for the condensation reaction, and a composite polyester composition containing the resulting polyester is also preferably used. In addition to the above-described organometallic compound, another compound may be mixed.

(polyester)
The composite polyester composition of the present invention contains a polyester obtained by mixing two or more polyhydric alcohols as described above, a polyhydric carboxylic acid, and a monohydric alcohol and condensing the mixture. The polyester obtained by condensing the mixture preferably includes a polyester represented by the following general formula (3) and a polyester represented by the following general formula (4).

Here, in the general formula (3), R represents an n-valent atomic group, R ¹ represents a (m + 1) -valent chain or cyclic aliphatic linking group or aromatic linking group, and R ² represents a substituent. An cycloalkyl group that may have a substituent, an alkenyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. Represents a good heteroaryl group. m represents an integer of 1 to 3, and when m is 2 or more, m R ^{2 s} may be the same or different. N represents an integer of 3 to 6, and n -OCOR ^1- (COOR ² ) _m may be the same or different.

  Moreover, it is preferable that at least 1 sort (s) of polyester obtained by this invention is represented by following General formula (4). In the present invention, it is preferable that the polyester represented by the general formula (3) and the polyester represented by the general formula (4) are mixed.

Here, in the general formula (4), R ′ represents an n-valent atomic group, R ³ represents an (m + 1) -valent chain or cyclic aliphatic linking group or aromatic linking group, and R ⁴ represents a substituted group. An alkyl group that may have a group, a cycloalkyl group that may have a substituent, an alkenyl group that may have a substituent, an aryl group that may have a substituent, or a substituent Represents a good heteroaryl group. m represents an integer of 1 to 3, and when m is 2 or more, m R ^{4 s} may be the same or different. N represents an integer of 2 to 6, and n -OCOR ^3- (COOR ⁴ ) _m may be the same or different. In addition, R in the general formula (3), R ′ in the general formula (4), R ¹ in the general formula (3), R ^{3 in} the general formula (4), R ² in the general formula (3) And any of R ^{4 in} the general formula (4) is different.

  In the general formula (3), R represents a trivalent to hexavalent atomic group. In general formula (3), n is preferably an integer of 3 to 6, more preferably an integer of 3 to 5, and further preferably an integer of 3 or 4.

  In the general formula (4), R ′ represents a divalent to hexavalent atomic group. In general formula (4), n is preferably an integer of 2 to 6, more preferably an integer of 2 to 4, and still more preferably an integer of 3 or 4.

  In the general formulas (3) and (4), m represents an integer of 1 to 3, and preferably represents an integer of 1 or 2. That is, the polyvalent carboxylic acid is preferably a divalent or trivalent polyvalent carboxylic acid.

  In the general formulas (3) and (4), the number of carbon atoms of R and R ′ is preferably independently 2 to 20, more preferably 2 to 15, and further preferably 2 to 10. It is preferably 2-7, more preferably 3-5.

  The atoms constituting the atomic groups R and R ′ are preferably each independently a carbon, hydrogen, or oxygen atom. R and R ′ are each independently an aliphatic hydrocarbon group that may have a substituent or an aromatic hydrocarbon group that may have a substituent. Especially, it is especially preferable that R and R ′ are each independently an atomic group composed of a saturated aliphatic hydrocarbon which may have a substituent. By setting R and R ′ as described above, a composite polyester composition having excellent lubricating performance can be obtained.

In the general formulas (3) and (4), R ¹ and R ³ each independently represent a residue of a polyvalent carboxylic acid. Here, the residue of the polyvalent carboxylic acid refers to a group constituting a part obtained by removing the carboxyl group from the polyvalent carboxylic acid. In particular, R ¹ and R ³ are preferably each independently a dimer acid residue, a trimer acid residue or an erucic acid dimer residue.

The number of carbon atoms of R ¹ and R ³ is preferably 7 or more, more preferably 14 or more, and further preferably 20 or more. The number of carbon atoms of R ¹ and R ³ is preferably 64 or less, more preferably 58 or less, and even more preferably 46 or less. Of these, the carbon number of the carbon atoms of R ¹ and R ³ is preferably 20 to 46.

In the general formulas (3) and (4), R ² and R ⁴ may each independently have an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, or a substituent. A good alkenyl group, an aryl group which may have a substituent, and a heteroaryl group which may have a substituent are represented. Specific examples of the group that R ² and R ⁴ can take include the group represented by ^Ra in the general formula (1). In addition, the substituent of each group that R ² and R ⁴ may have is not particularly limited. As the substituent, the above substituents can be exemplified similarly.

R ² and R ⁴ are preferably each independently a group having an oxyalkylene structure. That is, R ² and R ⁴ are preferably a branched alkyl group or an alkyl group containing an ether bond in the chain. Further, R ² and R ⁴ preferably have 3 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more.

  In the present invention, the polyester contains the polyester represented by the general formula (3) and two or more polyesters represented by the general formula (4), thereby dispersibility of the composite polyester composition in the base oil. Can be increased. By diversifying the shape of the polyester obtained by condensation, the packing between the polyesters can be suppressed, and the dispersibility with respect to the base oil can be improved.

  When mixing polyhydric alcohol, polyhydric carboxylic acid and monohydric alcohol compound, the equivalent ratio of mixing polyhydric carboxylic acid with respect to polyhydric alcohol is 1 to 4, and with respect to polyhydric alcohol It is preferable that the equivalent ratio of mixing the monohydric alcohol is 0.5 to 5. That is, the mixing ratio is preferably polyhydric alcohol: polyhydric carboxylic acid: monohydric alcohol = 1: 1 to 4: 0.5 to 5. The mixing ratio is more preferably 1: 2.0 to 4: 1.5 to 5, and more preferably 1: 2.2 to 4: 2.5 to 5. In particular, since the side chain of the polyester is preferably end-capped, the total equivalent of the polyhydric alcohol and the monohydric alcohol is preferably the same or larger than the equivalent of the polyvalent carboxylic acid. Here, the equivalent of polyhydric alcohol is the total equivalent of two or more polyhydric alcohols.

  The composite polyester composition of the present invention preferably has a viscosity at 40 ° C. of 50 to 1650 mPas. The viscosity at 40 ° C. of the composite polyester composition is preferably 50 mPas or more, more preferably 70 mPas or more, and further preferably 100 mPas or more. The viscosity of the composite polyester composition at 40 ° C. is preferably 1650 mPas or less, more preferably 1200 mPas or less, and further preferably 1000 mPas or less. By setting the viscosity of the composite polyester composition within the above range, the coefficient of friction of the composite polyester composition can be kept low, thereby improving the lubrication performance.

  The composite polyester composition of the present invention also has an excellent feature that the increase in the coefficient of friction is small from the normal fluid lubrication or elastohydrodynamic lubrication region to the extreme pressure region. Such an excellent effect is considered to be obtained when the polyester obtained in the present invention has a three-dimensional structure in which side chains are arranged radially. The polyester obtained in the present invention comprises a polyhydric alcohol capable of radially arranging a side chain, a polyvalent carboxylic acid connected to the polyhydric carboxylic acid, and a monohydric alcohol serving as a terminal linking group of the polyvalent carboxylic acid. It is a composed compound. In the present invention, a polyhydric alcohol is used as a central atomic group and a side chain is provided, so that a large free volume can be ensured by the three-dimensional structure. Thereby, an increase in viscosity and friction coefficient can be suppressed even under high pressure.

  In this invention, in addition to predetermined polyester, you may further contain a light part. Here, the light component refers to a component having a low molecular weight, and refers to an ester obtained by reacting all carboxyl groups of a polyvalent carboxylic acid with a monohydric alcohol and a compound having a smaller molecular weight. The viscosity of the composite polyester composition can be further lowered by allowing a liquid having a lower viscosity, such as a light component, to coexist. Thereby, high lubrication performance can be exhibited under all conditions.

In the composite polyester composition of the present invention, the ratio between the predetermined polyester and the light component is not particularly limited. In the aspect utilized for the use of the lubricant, the content of the light component is preferably 50% by mass or less, more preferably 45% by mass or less, and 40% by mass or less with respect to the predetermined polyester. More preferably. In addition, although there is no restriction | limiting in particular about a lower limit, it is preferable that it is 15 mass% or more.
The ratio between the predetermined polyester and the light component can be achieved by controlling the charging ratio of the three raw materials in the production method described later. Moreover, it can also adjust to a preferable range by isolate | separating a light part by distillation etc. and mixing with the remaining polyester by arbitrary ratios.
The composition ratio between the predetermined polyester and the light component containing dimer diol can be calculated by measuring gel permeation chromatography (GPC). The light component is easy to distinguish because the peak of GPC analysis appears sharply and its intensity is large.

  In the present invention, unreacted COOH in the polyvalent carboxylic acid may remain in the side chain of the polyester contained in the composite polyester composition, and unreacted in the polyhydric alcohol or monohydric alcohol. Although OH may be present, if OH and COOH remain, the hydroxyl value and the acid value increase, which may be undesirable depending on the application (for example, the use of a lubricant). In such a case, OH and COOH in the polyester can be eliminated by separate acylation and / or esterification treatment, and the hydroxyl value and acid value can be reduced.

In order to eliminate OH in the polyester, it is possible to obtain a polyester in which OH remains in the side chain and then acylate at least a part thereof. In the acylation treatment, monobasic acid (R ¹ COOH) or monobasic acid anhydride ((R ¹ CO) ₂ O) is added to the polyester in which OH remains and heated to convert the remaining OH to OCOR ¹ It is a process to convert to. When the hydroxyl value is reduced by the acylation treatment, mixing with other oil-based media is preferable in terms of easy mixing.
Moreover, you may perform the process which lose | disappears COOH in polyester. For example, it can be esterified by treatment with diazomethane or the like.

The proportion of unreacted OH in the polyester can be determined by measuring ¹³ C-NMR. In the use of the lubricant, the residual ratio of OH in the polyester is preferably 0 to 40%, more preferably 0 to 35%, and further preferably 0 to 30%. In the same application, the acid value of the polyester (mg number of KOH required to neutralize 1 g of the sample) is preferably 0 to 50, more preferably 0 to 40, and 0 to 30. More preferably it is. However, it is not limited to this range.

(Method for producing composite polyester composition)
The composite polyester composition of the present invention can be obtained by charging at least three raw materials of the two or more kinds of polyhydric alcohols, polyhydric carboxylic acids and monohydric alcohols described above and dehydrating them. That is, the method for producing a composite polyester composition of the present invention comprises a step of mixing two or more polyhydric alcohols, a polycarboxylic acid and a monohydric alcohol to obtain a mixture, and dehydrating and condensing the mixture to obtain a polyester. Process. In the production process, two raw materials (for example, a polyhydric alcohol and a polyhydric carboxylic acid, or a polyhydric carboxylic acid and a monohydric alcohol) may be reacted first, and then the remaining raw materials may be reacted.

  The charging ratio (mixing ratio) of the polyhydric alcohol, polyhydric carboxylic acid and monohydric alcohol is determined by an equivalent amount. The equivalent here means the chemical equivalent of COOH or OH in the reaction. When the number of OH in one molecule of the polyhydric alcohol is n and the number of moles is M1, the equivalent of the polyhydric alcohol is defined as n × M1. Similarly, when the number of COOH in one molecule of the polycarboxylic acid is m and the number of moles is M2, the equivalent of the polyvalent carboxylic acid is defined as m × M2. Since monohydric alcohol has one OH in one molecule, M3 is defined as M3. The above ratio is a ratio of these n × M1, m × M2, and M3.

  In the present invention, the mixing ratio is preferably polyhydric alcohol: polycarboxylic acid: monohydric alcohol = 1: 1 to 4: 0.5 to 5. The mixing ratio is more preferably 1: 2.0 to 4: 1.5 to 5, and more preferably 1: 2.2 to 4: 2.5 to 5. In particular, since the side chain of the polyester is preferably end-capped, the total equivalent of the polyhydric alcohol and the monohydric alcohol is preferably the same or larger than the equivalent of the polyvalent carboxylic acid.

  The composite polyester composition of the present invention can be obtained by subjecting the mixture charged as described above to a dehydration condensation reaction in the presence or absence of a catalyst.

  In the dehydration condensation, it is desirable to heat or to make an appropriate amount of a solvent azeotropic with water exist. Thereby, dehydration proceeds smoothly without coloring the product. This solvent is preferably a hydrocarbon solvent having a boiling point of 100 to 200 ° C, more preferably a hydrocarbon solvent having a boiling point of 100 to 170 ° C, and most preferably a hydrocarbon solvent having a boiling point of 110 to 160 ° C. Examples of these solvents include toluene, xylene, mesitylene and the like. If the amount to be added is too large, the liquid temperature will be in the vicinity of the solvent, and dehydration condensation will not proceed easily. On the other hand, if the amount is too small, azeotropy does not go smoothly. Therefore, the addition amount is preferably 1 to 25 mass%, more preferably 2 to 20 mass%, particularly preferably 3 to 15 mass%, based on the total amount of the polyhydric alcohol, polyvalent carboxylic acid and monohydric alcohol. -12 mass% is also preferable.

  Although the reaction is accelerated by using the catalyst, it is desirable not to use it because the post-treatment of removing the catalyst is complicated and causes coloring of the product. However, when used, normal conditions and procedures are used with normal catalysts. In this regard, reference can be made to Japanese Patent Publication Nos. 2001-501989, 2001-500499, 2001-507334, and 2002-509563.

  After completion of the preparation, the reaction is performed at a liquid temperature of 120 to 250 ° C, preferably 130 to 230 ° C, more preferably 130 to 220 ° C, and particularly preferably 140 to 220 ° C. As a result, a solvent containing water is azeotroped, cooled at a cooling site such as Dean Stark, and becomes a liquid to separate water and the solvent. This water may be removed.

  As for the reaction time, since the theoretically generated water amount is calculated from the number of moles charged, it is preferable to carry out the reaction until the water amount is obtained, but it is difficult to complete the reaction completely. Even if the reaction is terminated when the theoretical water generation amount is 60 to 90%, the lubricity of the composite polyester composition is good. The reaction time is 1 to 24 hours, preferably 3 to 18 hours, more preferably 5 to 18 hours, and most preferably 6 to 15 hours.

After dehydration condensation and removal of volatile matter, the remaining OH may be acylated. When acylating, a suitable amount of monobasic acid (R ¹ COOH) or monobasic acid anhydride ((R ¹ CO) ₂ O), preferably monobasic acid anhydride ((R ¹ CO) ₂ O) is added Preferably, at least a part, preferably almost all of the remaining OH can be converted to OCOR ¹ by heating at 100 ° C. or higher, more preferably 120 ° C. or higher, particularly 150 ° C. or higher. It is preferable to remove the by-product volatile matter by distillation described later. R ¹ is an alkyl group or aryl group having 1 to 10 carbon atoms, preferably an alkyl group or aryl group having 1 to 6 carbon atoms, and is a methyl group, ethyl group, butyl group, or phenyl group. Are more preferable, a methyl group or a phenyl group is preferable, and a methyl group is particularly preferable.

  Further, after dehydration condensation and removal of volatile matter, an esterification treatment may be performed in order to eliminate the remaining COOH. The esterification treatment can be performed, for example, by adding diazomethane, and at least a part, preferably almost all of COOH can be converted into a methyl ester.

  By this reaction, a composite polyester composition containing a predetermined polyester and a soft component containing at least the ester produced as described above is obtained. After the dehydration-condensation reaction, if desired, after acylation treatment and / or esterification treatment, the resulting composite polyester composition can be used as it is for various uses, for example, as a lubricant. Various processes may be performed depending on the application.

  After completion of the reaction and the treatment after the reaction, it is preferable to perform filtration to remove dust and the like. When the composite polyester becomes solid, it can be melted out or taken out as a powder by reprecipitation.

(Composition)
The present invention may relate to a composition containing at least a composite polyester composition. For example, the composite polyester composition of the present invention and various additives and / or media can be added to the composition.
Examples of additives include antiwear agents, viscosity index improvers, antioxidants, detergents, dispersants, flow agents, curing agents, corrosion inhibitors, seal conformers, antifoaming agents, rust inhibitors, and corrosion inhibitors. , One or more selected from friction modifiers and thickeners.
By adding such an additive, a preferable function as a lubricant such as wear suppression can be imparted. Regarding the lubricant that can be used in the present invention, the description in paragraphs [0098] to [0165] of JP2011-89106A can be referred to.

Examples of the medium include one or more selected from mineral oils, fat compounds, polyolefin oils, silicone oils, perfluoropolyether oils, aromatic ester oils, and polyol ester lubricating oils.
In the present invention, the “medium” means all the media generally called “fluid liquids”. However, it is not necessary to be liquid at room temperature or the temperature used, and any form of material such as solid and gel can be used in addition to liquid. There is no restriction | limiting in particular about the medium utilized in this invention, According to a use, it can select from various liquids. Regarding the medium that can be used in the present invention, the description in paragraphs [0067] to [0096] of JP-A-2011-89106 can be referred to.

As a medium, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and / or vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, and sulfuric acid washing. It is also preferable to use a hydrocarbon base oil that has been refined by combining one or more of the refining treatments such as white clay treatment alone or in combination of two or more.
As the hydrocarbon base oil, the ratio (CA / CB) of the ratio (CA) of components having 24 or less carbon atoms and the ratio (CB) of components having 25 or more carbon atoms in the carbon number distribution obtained by gas chromatographic distillation is 2. It is preferred that a base oil of 0.0 or more is used. CA / CB is preferably 2.5 or more, more preferably 3 or more, and most preferably 5 or more. By setting CA / CB within the above range, a sufficiently low high temperature high shear (HTHS) viscosity at 80 ° C. can be obtained.

  Hydrocarbon base oil having a ratio CC / CD of 0.3 or less of the ratio (CC) of components having 18 or less carbon atoms and the ratio (CD) of components having 19 or more carbon atoms obtained by gas chromatographic distillation. It is preferable that Preferably, CC / CD is 0.25 or less, more preferably 0.2 or less, and most preferably 0.1 or less. By setting CC / CD within the above range, the consumption of lubricating oil can be suppressed even in the generator engine.

The gas chromatographic distillation here was carried out under the following conditions.
Model: GC-2010 manufactured by Shimadzu Corporation
Column: Ultra Alloy-1HT (30mm x 0.25mmΦ)
Carrier gas: Helium 200kPa
Detector: FID
Det. Temp. : 350 ° C
Oven Temp. : 80 ° C. to 320 ° C. (5 min)
Temp. Rate: 5 ° C / min
Inj. Vol: 1 μL toluene solution

As a medium, the following base oils (1) to (8) are used as raw materials, and the raw oil and / or a lubricating oil fraction recovered from the raw oil is refined by a predetermined refining method, A mineral oil base oil obtained by recovering the fraction can also be used.
(1) Distilled oil by atmospheric distillation of paraffinic crude oil and / or mixed base crude oil (2) Distilled oil by vacuum distillation of atmospheric distillation residue of paraffinic crude oil and / or mixed base crude oil ( WVGO)
(3) Wax (slack wax, etc.) obtained by the lubricant dewaxing process and / or synthetic wax (Fischer-Tropsch wax, GTL wax, etc.) obtained by the gas-to-liquid (GTL) process, etc.
(4) One or two or more mixed oils selected from base oils (1) to (3) and / or mild hydrocracked oils of the mixed oils (5) selected from base oils (1) to (4) 2 or more kinds of mixed oils (6) Base oil (1), (2), (3), (4) or (5) debris oil (DAO)
(7) Mild hydrocracking treatment oil (MHC) of base oil (6)
(8) Two or more mixed oils selected from base oils (1) to (7).

  The above-mentioned predetermined purification methods include hydrorefining such as hydrocracking and hydrofinishing; solvent refining such as furfural solvent extraction; dewaxing such as solvent dewaxing and catalytic dewaxing; acid clay and activated clay White clay refining; chemical (acid or alkali) cleaning such as sulfuric acid cleaning and caustic soda cleaning are preferred. In the present invention, one of these purification methods may be performed alone, or two or more may be combined. Moreover, when combining 2 or more types of purification methods, the order in particular is not restrict | limited, It can select suitably.

Furthermore, as the medium, the following base oil (9) or the following base oil (9) obtained by performing a predetermined treatment on the base oil selected from the base oils (1) to (8) or the lubricating oil fraction recovered from the base oil (10) is particularly preferred.
(9) The base oil selected from the base oils (1) to (8) or the lubricating oil fraction recovered from the base oil is hydrocracked and recovered from the product or the product by distillation or the like. Hydrocracked mineral oil obtained by performing dewaxing treatment such as solvent dewaxing or catalytic dewaxing on the lubricating oil fraction, or distillation after the dewaxing treatment (10) The above base oils (1) to (8) ) Or a lubricating oil fraction recovered from the base oil is hydroisomerized, and the product or the lubricating oil fraction recovered from the product by distillation or the like is subjected to solvent dewaxing or catalytic dewaxing. Hydroisomerized mineral oil obtained by performing a dewaxing process such as or by distillation after the dewaxing process.

  Further, when obtaining the medium of the above (9) or (10), a solvent purification treatment and / or a hydrofinishing treatment step may be further provided as necessary at an advantageous step.

The kinematic viscosity at 100 ° C. of the mineral base oil is preferably 4.5 mm ² / s or less, more preferably 4 mm ² / s or less, still more preferably 3.5 mm ² / s or less, and most preferably 3 mm ² / s. s or less. On the other hand, the kinematic viscosity at 100 ° C. is preferably 1 mm ² / s or more, more preferably 1.5 mm ² / s or more, still more preferably 2 mm ² / s or more, and most preferably 2.3 mm ² / s or more. It is.
The kinematic viscosity at 100 ° C. here refers to the kinematic viscosity at 100 ° C. as defined in ASTM D-445.

As the medium, it is preferable to use a mineral oil base oil having a kinematic viscosity at 100 ° C. within the following range by distillation or the like. It is possible to use a mixture of (I) and (II), but it is preferable to use (I) alone.
(I) Mineral oil base oil (II) 100 having a kinematic viscosity at 100 ° C. of 1 mm ² / s or more, preferably 2.3 mm ² / s or more and less than 3 mm ² / s, preferably 2.9 mm ² / s or less. Mineral base oil having a kinematic viscosity at 3 ° C. of 3 mm ² / s or more, preferably 3.5 mm ² / s or more, 4.5 mm ² / s or less, preferably 4.0 mm ² / s or less

The mineral oil base oil preferably has a viscosity index of 90 or more, more preferably 105 or more, and still more preferably 110 or more. Moreover, it is preferable that it is 160 or less. Further, the viscosity index of the mineral oil base oil (I) is preferably 90 or more, more preferably 105 or more, still more preferably 110 or more, and most preferably 120 or more. Moreover, 160 or less is preferable. Further, the viscosity index of the mineral oil base oil (II) is preferably 110 or more, more preferably 120 or more, still more preferably 130 or more, and most preferably 140 or more. Moreover, 160 or less is preferable. By setting the viscosity index of the mineral base oil within the above range, the degree-temperature characteristics, heat / oxidation stability, and volatilization prevention properties are improved, and wear prevention properties are improved.
In addition, the viscosity index as used in the field of this invention means the viscosity index measured based on JISK2283-1993.

Further, the density (ρ ₁₅ ) of the mineral base oil at 15 ° C. depends on the viscosity grade of the lubricating base oil component, but is not more than the value of ρ represented by the following formula, that is, ρ ₁₅ ≦ ρ. Is preferred.
ρ = 0.0025 × kv100 + 0.816
In the formula, kv100 represents the kinematic viscosity (mm ² / s) of the lubricating base oil component at 100 ° C.

By setting the density (ρ ₁₅ ) of the mineral oil base oil at 15 ° C. within the above range, the viscosity-temperature characteristics and thermal / oxidation stability, as well as the volatilization prevention and low-temperature viscosity characteristics can be improved. Can save fuel.

Specifically, the density (ρ ₁₅ ) at 15 ° C. of the mineral oil base oil is preferably 0.835 or less, more preferably 0.828 or less, still more preferably 0.822 or less, and particularly preferably 0.815 or less. Most preferably, it is 0.805 or less, and preferably 0.785 or more. In addition, the density in 15 degreeC said by this invention means the density measured in 15 degreeC based on JISK2249-1995.

(Property of composition)
The composition of the present invention preferably has a viscosity at 40 ° C. of 1650 mPa · s or less, more preferably 1200 mPa · s or less, and even more preferably 1000 mPa · s or less. Viscosity needs to be adjusted to an appropriate viscosity depending on the usage environment.

In the composition of the present invention, the constituent elements are preferably composed of carbon, hydrogen, oxygen and silicon. Even if the composition of this invention does not contain phosphorus and sulfur, it can exhibit the same or better performance.
The oil used as the oily medium is also preferably composed of carbon, hydrogen, oxygen and silicon. The current lubricating oil usually contains phosphorus, sulfur and heavy metals. Lubricating oil used in a two-stroke engine that also burns lubricating oil together with fuel does not include phosphorus and heavy metals in consideration of environmental impact, but sulfur is included in about half of the lubricating oil used in a four-stroke engine. Yes. In other words, with the current lubrication technology, it is inferred that the formation of a boundary lubrication film with a sulfur content is indispensable. However, since it contains elemental sulfur, the load on the catalyst for exhaust gas purification is extremely high. large. Platinum and nickel are used for the exhaust gas purification catalyst, but the poisoning action of phosphorus and sulfur is a serious problem. From this point of view, the merit that the elements constituting the lubricating oil composition do not contain phosphorus or sulfur is very large. Furthermore, the absence of phosphorus and sulfur is optimal for industrial machinery other than engine oil, especially for lubricating oil in food production equipment. In the current technology, the elemental composition is taken into consideration for the environment at the expense of the friction coefficient. This is also a very preferable technique for metal cutting and machining lubricants that require a large amount of water for cooling.

(Method for preparing composition)
The composition of the present invention can be prepared by adding the complex polyester composition in an oily medium or an aqueous medium, and dissolving and / or dispersing it. Dissolution and / or dispersion may be performed under heating. The amount of the composite polyester composition added is preferably 10% by mass or more with respect to the mass of the oily medium. However, it is not limited to this range, and may be outside the above range as long as the compound is an amount sufficient to exhibit a friction reducing action.

(Use of composition)
The composition of the present invention is useful as a lubricant. That is, the present invention also relates to a lubricant including the above-described composite polyester composition or the above-described composition.
The lubricant of the present invention is supplied, for example, between two sliding surfaces, and can be used to reduce friction. The composition of the present invention can form a film on the sliding surface. As for the material of the sliding surface, in steel, specifically, carbon steel for machine structure, alloy steel for structural machinery such as nickel chrome steel, nickel chrome molybdenum steel, chrome steel, chrome molybdenum steel, aluminum chrome molybdenum steel, Examples include stainless steel and multi-aged steel.

As the material of the sliding surface, various metals other than steel, or inorganic or organic materials other than metals are widely used. Examples of inorganic or organic materials other than metals include various plastics, ceramics, carbon, etc., and mixtures thereof. More specifically, examples of the metal material other than steel include cast iron, copper / copper-lead / aluminum alloy, castings thereof, and white metal.
In addition, about the material of a sliding surface, description of Paragraph [0168]-[0175] of Unexamined-Japanese-Patent No. 2011-89106 can be referred.

  The lubricant of the present invention can be used for various applications. For example, lubricating oil for grease, release agent, engine oil for internal combustion engine, oil for metal processing (cutting), oil for bearing, fuel for combustion engine, vehicle engine oil, gear oil, hydraulic oil for automobile, ship / aircraft Lubricant, machine oil, turbine oil, bearing oil, hydraulic fluid, compressor / vacuum pump oil, refrigerator oil, metalworking lubricant, magnetic recording medium lubricant, micromachine lubricant, artificial bone lubricant It can be used as an agent, shock absorber oil or rolling oil. It is also used for air conditioners and refrigerators with reciprocating and rotary hermetic compressors, automotive air conditioners and dehumidifiers, freezers, refrigerated warehouses, vending machines, showcases, chemical plant and other cooling devices. .

As a lubricant for metal processing that does not contain chlorine compounds, for example, when hot rolling metal materials such as steel materials and Al alloys, or when performing processing such as cutting, cold rolling oil of aluminum, cutting oil, As metal processing oil such as grinding oil, drawing oil, press processing oil and plastic processing oil of metal, especially as a deterrent for wear, breakage and surface roughness during high speed and high load processing, as well as broaching and gun drilling It is also useful as a metal working oil composition that can be applied to low speed and heavy cutting.
Further, it can be used for various grease lubricants, magnetic recording medium lubricants, micromachine lubricants, artificial bone lubricants, and the like. In addition, since the elemental composition of the composition can be a carbohydrate, for example, polyoxyethylene ether widely used in cake mix, salad dressing, shortening oil, chocolate, etc. as an emulsifying, dispersing or solubilizing agent is used. By using the composition of the sorbitan fatty acid ester containing edible oil as the base oil as the lubricating oil, a high-performance lubricating oil that is completely harmless to the human body can be used for lubrication of food production line manufacturing equipment and medical equipment members.
Furthermore, the composition of the present invention can be used as cutting oil or rolling oil by emulsifying and dispersing it in an aqueous system or by dispersing it in a polar solvent or a resin medium.

Moreover, the composition of this invention can be utilized for various uses also as a mold release agent. For example, polycarbonate resin, flame retardant polycarbonate resin, crystalline polyester resin which is the main component of image forming toner used in electrophotographic apparatus and electrostatic recording apparatus, various molding thermoplastic resin compositions and semiconductor encapsulating Used as a mold release agent for epoxy resin compositions. One embodiment of the release agent is an embodiment containing 0.01 to 10 parts by mass (preferably 0.1 to 5 parts by mass) of the composite polyester composition with respect to 100 parts by mass of a resin such as a polycarbonate resin.
Moreover, it can also be used as an antifouling agent for preventing the soiling of the textile product by kneading or applying to the textile product such as clothing in advance to promote the removal of the soiling attached to the textile product.

The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below .

(Examples 1-33 and Comparative Examples 1-5)
<Synthesis of polyester>
Component A, Component B, and Component C described in Table 1 were charged into a reaction vessel equipped with a Dean-Stark dehydrator so as to have a molar equivalent ratio described in Table 1. Then, it stirred at liquid temperature 160-200 degreeC for 12 hours. Water generated during stirring was removed. The mixture was cooled to room temperature to obtain a polyester composition (Chemical Formulas 1-33 and Ratio-1-4) as a yellow to transparent liquid. In addition, in component A, component B, and component C shown in Table 1, CA-26 is Tsunodai 395 manufactured by Tsukino Foods Co., Ltd., CA-27 is Tsunodim 346 manufactured by Tsukuno Foods Co., Ltd., and CA-28 is Prepol 1004 manufactured by Croda. The other raw materials were those manufactured by Wako Pure Chemical Industries. In Table 1, CA-29 represents erucic acid (CAS No. 112-86-7, manufactured by Wako Pure Chemical Industries, Ltd.).

<Preparation 1 of composite polyester composition>
Each polyester composition (Chemical Formulas 1 to 33 and ratios -1 to 5) and mineral oil (100 neutral oil, viscosity 4.4 mm / s ^{2 at} 100 ° C.) were mixed at an arbitrary ratio to prepare a lubricant. . The dispersibility of the lubricant was measured by the following method. The results are shown in Table 1.

<Evaluation 1: Dispersion performance>
When adjusting 100 parts by mass of two kinds of lubricants so that the mixing ratio of the polyester composition and mineral oil was 1/99 and 30/70, the time until the liquid was uniformly mixed was visually evaluated. .
If the dispersibility of the polyester composition in the base oil is high, the polyester composition can be mixed and uniformly dispersed in an arbitrary amount. That is, even when the mixing ratio of the mineral oil to the polyester is small or large, both can be uniformly dispersed in the same mixing time without separation. Then, when adjusting a lubricant so that the mixing ratio of a polyester composition and mineral oil might be set to 1/99 or 30/70, the time difference until visual mixing confirmation was measured. The evaluation criteria are as follows. In addition, the thing of evaluation more than B rank was set as the pass. The results are shown in Table 1 below.
Rank A: Time difference until visual mixing confirmation is less than 10 seconds Rank B: Time difference until visual mixing confirmation is 10 seconds or more and less than 30 seconds C Rank: Time difference until visual mixing confirmation is 30 seconds or more and less than 1 minute D Rank: Visual mixing Time difference until confirmation is 1 minute or more and less than 3 minutes E rank: Time difference until visual mixing confirmation is 3 minutes or more

<Preparation 2 of composite polyester composition>
Each polyester composition obtained in Examples and Comparative Examples (Chemical Formulas 1 to 33 and Ratios -1 to 5) and mineral oil (100 neutral oil, viscosity 4.4 mm / s ^{2 at} 100 ° C.) are mass ratios. The lubricant was adjusted by mixing at 25/75. The lubricating performance of the lubricant was measured by the following method. The results are shown in Table 1.

<Evaluation 2: Lubrication performance>
Evaluation assuming extreme pressure conditions was performed using a vibration type frictional wear tester (manufactured by Optimol Instruments Prutechnik GmbH, trade name: SRV4), using a vibration frequency of 100 Hz, a vibration width of 2.0 mm, a load of 30 N, a temperature of 60 ° C., Test piece: The test was performed by measuring the coefficient of friction at a point contact (ball) and a test time of 30 minutes.
Generally, the friction coefficient obtained on the assumption of extreme pressure conditions is obtained as a value larger than the friction coefficient in a normal fluid lubrication region or elastohydrodynamic lubrication region. For this reason, those having a small coefficient of friction under extreme pressure conditions and good evaluation below naturally have a small coefficient of friction in a normal fluid lubrication region and elastohydrodynamic lubrication region, and the evaluation is good. In addition, the evaluation is C grade or higher. Table 1 below shows the evaluation results of the coefficient of friction using an SRV4 testing machine assuming extreme pressure conditions.
Rank A: Friction coefficient <0.050
B rank: 0.050 ≦ friction coefficient <0.053
C rank: 0.053 ≦ coefficient of friction <0.060
D rank: 0.060 ≦ friction coefficient <0.070
E rank: Friction coefficient ≧ 0.070

As can be seen from Table 1, the composite polyesters of Examples 1 to 33 are excellent in dispersibility in the base oil and exhibit excellent lubricating performance.
On the other hand, it can be seen that the composite polyester compositions of Comparative Examples 1 to 5 are not sufficiently dispersible in the base oil. Moreover, in Comparative Examples 1 and 3, in addition to the poor dispersibility in the base oil, it can be seen that the lubricating performance is not sufficiently exhibited.

(Examples 34 to 38)
<Preparation of composite polyester composition>
A polyester composition and an organometallic compound shown in Table 2 were mixed with a base oil (100 neutral oil, viscosity 4.4 mm / s ^{2 at} 100 ° C.) at a ratio shown in Table 2 to prepare a lubricant. The dispersion performance and lubrication performance of the lubricant were measured by the following methods. The results are shown in Table 2.

  As can be seen from Table 2, the dispersibility and lubricity of the lubricants of Examples 34 to 38 are all good regardless of the type of the organometallic compound.

  According to the present invention, a composite polyester composition capable of exhibiting excellent lubricating performance can be obtained. Furthermore, the composite polyester composition of the present invention can exhibit excellent dispersibility with respect to the base oil. Thus, the composite polyester composition of the present invention has high lubricating performance and dispersibility, and has high industrial applicability.

Claims (24)

Including a polyester obtained by condensing two or more polyhydric alcohols, polyhydric carboxylic acid and monohydric alcohol,
At least one of the two or more polyhydric alcohols is a polyhydric alcohol containing three or more hydroxyl groups ,
The composite polyester lubricant composition whose carbon number of the said polyhydric carboxylic acid is 24-48 .   The composite polyester lubricant composition according to claim 1, wherein at least one of the two or more polyhydric alcohols is a saturated aliphatic alcohol.   The composite polyester lubricant composition according to claim 1 or 2, wherein at least one of the two or more polyhydric alcohols is selected from pentaerythritol, trimethylolpropane, glycerin, or dipentaerythritol.   The said 2 or more types of polyhydric alcohol contains the 1st polyhydric alcohol containing 3-6 hydroxyl groups, and the 2nd polyhydric alcohol containing 2-6 hydroxyl groups. 2. The composite polyester lubricant composition according to item 1.   The first polyhydric alcohol is a polyhydric alcohol containing 3 or 4 hydroxyl groups, and the second polyhydric alcohol is a polyhydric alcohol containing 2 to 4 hydroxyl groups. A composite polyester lubricant composition. The composite polyester lubricant composition according to any one of claims 1 to 5, wherein the polyvalent carboxylic acid is a dibasic acid or a tribasic acid of an unsaturated fatty acid. The composite polyester lubricant composition according to any one of claims 1 to 6, wherein the polyvalent carboxylic acid is dimer acid, trimer acid or erucic acid dimer. The composite polyester lubricant composition according to any one of claims 1 to 7, wherein the monohydric alcohol has 6 or more carbon atoms. The composite polyester lubricant composition according to any one of claims 1 to 8, wherein the monohydric alcohol has at least one oxyalkylene group. The said monohydric alcohol is a composite polyester lubricant composition of any one of Claims 1-9 represented by following General formula (1).
(In general formula (1), R ^a has an alkyl group which may have ^a substituent, ^a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An aryl group which may be substituted or a heteroaryl group which may have a substituent, wherein X ^a1 and X ^a2 each independently represents a hydrogen atom, a halogen atom or an alkyl group, and na 1 represents an integer of 1 to 4. Na2 represents an integer of 1 to 12. When na1 is 2 or more, the na1 X ^a1 may be the same or different, and the na1 X ^a2 may be the same or different. In addition, when na2 is 2 or more, na2 — (O (CX ^a1 X ^a2 ) _na1 — may be the same or different). The composite polyester lubricant composition according to any one of claims 1 to 10, further comprising at least one organometallic compound of an organomolybdenum compound and an organozinc compound. The organometallic compound includes sulfurized oxymolybdenum-N, N-di-octyldithiocarbamate, sulfurized oxymolybdenum-N, N-di-tridecyldithiocarbamate, zinc n-butyl-n-pentyldithiophosphate, di-2- The composite polyester lubricant composition according to claim 11 , which is zinc ethylhexyldithiophosphate or zinc isopropyl-1-ethylbutyldithiophosphate. The polyester is mixed and condensed so that the equivalent ratio of the polyhydric carboxylic acid is 1 to 4 and the equivalent ratio of the monohydric alcohol is 0.5 to 5 with respect to the polyhydric alcohol. The composite polyester lubricant composition according to any one of claims 1 to 12, obtained by :   The polyester is mixed and condensed so that the equivalent ratio of the polyhydric carboxylic acid is 2.2 to 4 and the equivalent ratio of the monohydric alcohol is 2.5 to 5 with respect to the polyhydric alcohol. The composite polyester lubricant composition according to claim 1, wherein the composite polyester lubricant composition is obtained.   The polyester is mixed and condensed so that the equivalent ratio of the polyhydric carboxylic acid is 2.2 to 4 and the equivalent ratio of the monohydric alcohol is 2.5 to 5 with respect to the polyhydric alcohol. The composite polyester lubricant composition according to claim 1, wherein the composite polyester lubricant composition is obtained. The composite polyester lubricant composition according to any one of claims 1 to 15, wherein the polyester includes a polyester represented by the following general formula (3) and a polyester represented by the following general formula (4).
(In general formula (3), R represents an n-valent atomic group, R ¹ represents a (m + 1) -valent chain-like or cyclic aliphatic linking group or aromatic linking group, and R ² has a substituent. An alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an alkenyl group that may have a substituent, an aryl group that may have a substituent, or a hetero that may have a substituent Represents an aryl group, m represents an integer of 1 to 3, and when m is 2 or more, m R ^{2 s} may be the same or different, and n represents an integer of 3 to 6 , N -OCOR ^1- (COOR ² ) _m may be the same or different.)
(In General Formula (4), R ′ represents an n-valent atomic group, R ³ represents an (m + 1) -valent chain-like or cyclic aliphatic linking group or aromatic linking group, and R ⁴ represents a substituent. It may have an alkyl group that may have, a cycloalkyl group that may have a substituent, an alkenyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. Represents a heteroaryl group, m represents an integer of 1 to 3, and when m is 2 or more, m R ^{4 s} may be the same or different, and n represents an integer of 2 to 6 N-OCOR ³ — (COOR ⁴ ) _m may be the same or different, and R in the general formula (3), R ′ in the general formula (4), and the general formula ( 3) R ¹ in general formula (4), R ³ in general formula (4), R ² in general formula (3) and R ⁴ in general formula (4) are different.   In the said General formula (3) and (4), R and R 'are respectively independently the atomic group which consists of a saturated aliphatic hydrocarbon which may have a substituent. Composition. In the general formula (3) and (4), the R ¹ and R ³ are independently, the composite polyester lubricant according to claim 16 or 17 dimer acid residues, trimers acid residue or erucic acid dimer residues Agent composition. In the general formula (3) and (4), R ² and R ⁴ are each independently, a composite polyester lubricant composition according to any one of claims 16 to 18 is a group having an oxyalkylene structure.   The composite polyester lubricant composition according to any one of claims 1 to 19, which has a viscosity at 40 ° C of 50 to 1650 mPas.   The composite polyester lubricant composition according to any one of claims 1 to 20, an antiwear agent, a viscosity index improver, an antioxidant, a detergent, a dispersant, a flow, a curing agent, a corrosion inhibitor, and a seal. A lubricant composition containing one or more additives selected from a compatibility agent, an antifoaming agent, a rust inhibitor, a corrosion inhibitor, a friction modifier, and a thickener.   The composite polyester lubricant composition according to any one of claims 1 to 20, or the composition according to claim 21, and mineral oil, oil compound, polyolefin oil, silicone oil, perfluoropolyether oil, aroma. A lubricant composition containing at least one group oil selected from a group ester oil and a polyol ester lubricating oil.   A lubricant comprising the composite polyester lubricant composition according to any one of claims 1 to 20, or the lubricant composition according to claim 21 or 22.   Grease lubricants, mold release agents, engine oils for internal combustion engines, metal processing (cutting) oils, bearing oils, combustion engine fuels, vehicle engine oils, gear oils, automotive hydraulic oils, marine and aircraft lubricants Oil, machine oil, turbine oil, bearing oil, hydraulic oil, compressor / vacuum pump oil, refrigerator oil, metalworking lubricant, magnetic recording medium lubricant, micromachine lubricant, artificial bone lubricant, The lubricant according to claim 23, which is used as a shock absorber oil or a rolling oil.